1-nitro-3-alkylanthrapyridone compounds and process for their preparation



Patented Apr. 6, 1948 UNITED STATES PATENT OFFICE.

1-NITRO3-ALKYLANTHRAPYRIDONE COM- POUNDS AND PROCESS FOR THEIR PREP-ARATION Charles V. Wilson, Rochester, N. Y., assignor to Eastman KodakCompany, Rochester, N. Y., a corporation of New Jersey No Drawing.Application October 26, 1946, Serial No; 706,069

11 Claims.

1 This invention relates to a process for preparing 1-nitro-3-alkylanthrapyridone compounds and to1-nitro-3-a1kylanthrapyridone compounds as new products. 7

I have discovered that, new anthrapyridone compounds having the generalformula:

group can be prepared by reacting an anthraquinone compound having thegeneral formula:

wherein R, X and Y have the meaning above given and Z represents abromine atom, a chlorine atom or an iodine atom with an alkali metalnitrite in the presence of a liquid diluent which exerts a solventaction on the anthraquinone compound and is inert with respect to thereaction mixture. So far as I am aware the l-nitro-3-alkylanthrapyridone compounds obtained by my new process are newcompounds. As illustrated hereinafter they are useful as intermediatesfor the preparation of anthrapyridone dyes.

It is here noted that whenever the term alkyl is used herein inconnection with the alkyl group present in the 3-position of theanthrapyridone nucleus or with reference to the alkyl group attached tothe amino nitrogen atom present in the l-position of the anthraquinonestarting compound, it refers to an alkyl group having one to two carbonatoms, inclusive. 7

:For purposes of clarity, since various nomenclatures have been used inconnection with anthrapyridone, the anthrapyridone nucleus is numberedherein as follows:

This numbering is that used by Chemical Abstracts.

It is an object of my invention to provide a process for preparingl-nitro-S-alkylanthrapyridone compounds. Another object is to providenew 1-nitro-3-alky1anthrapyridone compounds.

Any of the alkali metal nitrites can be employed in the process of myinvention. However, from a practical viewpoint the use of sodium nitriteor potassium nitrite is preferred.

N' monohalogenoacetyl-N-alkyl 1 aninoan thraquinone compounds that canbe employed in my process include, for example, N-chloroacetyl-N-methyl-l-aminoanthraquinone, Nbromoacetyl-N-methyl-l-aminoanthraquinone,N-chl0roacetyl-N-methyl-l-amino 4 bromoanthraquinone,N-bromoacetyl-N-methyl-l-aminoi-b romoanthraquinone, N-iodoacetyl Nmethyl-1- aminoanthraquinone, N-bromoacetyl-N-methyl-I-amin0-4-chloroanthraquinone, N-chloroacetyl- N -methyl-l-amino 4chloroanthraquinone, N- iodoacetyl -j N methyl-1-amino-4-bromoanthraquinone, N-bromoacetyl N methyl-l-a nino-ehydroxyanthraquinone,N-bromoacetyl- N-ethyll-aminoanthraquinone,N-chloroacetyLN-ethyll-aminoanthraquinone N-iodoacetyl-N-methyl-1-amino-4-hydroxyanthraquinone, N-icdoacetyl-N-ethyl-l-aminoanthraquinone, N-bromoacetyl-N-methyl-1-amino-5-bromo-anthraquinone, N-

bromoacetyl-N-methyl-l-amino 5 hydroxyanthraquinone andN-chloroacetyl-N-methyl-1- amino-5-chloroanthraquinone.

Organic liquid diluents that can be employed in my new process include,for example, cellosolve (ethylene glycol monoethyl ether), methyl cellosolve (ethylene glycol monomethyl ether), butyl cellosolve (ethyleneglycol monobutyl ether), 3-

hydroxy-ethyl acetate, carbitol, methyl carbitol and butyl carbitol.Pyridine, a well known organic solvent, cannot be used.

The following examples, in which parts areexpressed by weight,illustrate the process and the compounds of my invention.

Example 1 To a warm solution of 3 parts ofN-bromoacetyl-N-methyl-l-aminoanthraquinone in 25.0 parts of ethyleneglycol monoethyl ether was added a concentrated aqueous solution of 1part of sodium nitrite. In a short time 1-nitro-3-methylanthrapyridoneseparated, It was recovered by Starting Compound ProductN-bromoacetyl-N-methy l-1-amino-4-chloroanthraquinoneN-bromoacetyl-N-ethyl-l-aminoanthraqumoneN-bromoacetyl-N-methyl-l-amino--bromoanthraqu1noneN-bromoacetyl-N-methyl-l-amino-5-hydroxyanthraqulnonN-bromoacetyl-N-methyl-l-amino-fi-chloroanthraquimoneN-bromoacety1-N-methyl-l-amino-4,5-d1hydroxyanthraqumoneN-chloroacctyl-N-ethyl-1-amino-4-hydroxyanthraqumoneN-chloroacctyl-N-ethyl-l-amino-4-chloroanthraqumoneN-chloroacetyl-N-ethyl-l-amino-G-hydroxyanthraqumonel-nitro-3-methyl-fi-chloro-anthrapyridone.

l-nitro-3-ethylanthrapyridone.

l-nitr0-3-n1ethyl-S-bromo-anthrapyridone.

l-nitro-R-methyl-8-hydroxyanthrapyridonc.

1-nitro-3-methyl-S-chloroanthrapyridone.

..- l-nitro-B-methyl-fi,S-dlhydroxyanthrapyridone.1-nitro-3-ethyl-6-hydroxy-anthrapyridone.l-nitro-3-ethyl-fi-chloro-anthrapyrldone.1-nitro-3-ethyl-8-hydroXy-anthrapyr1done.

aminoanthraquinone, which; after recrystallization from cellosolvemelted at 247 C.

An equivalentgram molecular weight of N- chloroacetyl-N-methy1-l-aminoanthraquinone or N-iodoacetyl Nmethyl-l-aminoanthraquinone can be substituted for the N-bromoacetyl-N-methyl-l-aminoanthraquinone of the foregoing example. The same reactionproduct is obtained.

Example 2 To a warm solution of 3.7 parts of N-bromoacetyl-N-methyl-1-amino-4-bromoanthraquinone in 50 parts of fi-h'ydroxyethylacetate was added a concentrated aqueous solution of 1 part of sodiumnitrite. In a short time 1-nitro-3-methyl-6- bromoanthrapyridoneseparated and. was recovered by fitration. Upon recrystallization fromnitrobenzene it is obtained as a light yellow colored solid melting at332 C.334 C.

Analysis: Calculatedfor C1'1H9BIN2O4Z Br, 20.8. Found: Br, 20.9.

An equivalent gram molecular weight of N-chloroacetyl-N-methyl-l-aminol-bromoanthraquinone or N-iodoacetyl e Nmethyl-l-aminol bromoanthraquinone can be substituted for theN-bromoacetyl N -,methyl-1 -amino-4-bromoanthraquinone of the foregoingexample. The same reaction product is obtained.

Example 3 To a solution of 3.5 parts of N-bromoacetyl-N- methyl 1amino-4-bromoanthraquinone in 70 parts of ethylene glycol monoethylether at 100-120 C. was added a solution of 1 part of potassium nitritein 5 parts of water. Shortly after the addition of the potassium nitritethe clear reaction mixture began to deposit crystals of 1 nitro-3-methyl6 bromoanthrapyridone. After cooling to room temperature the reactionproduct was recovered by filtration and recrystallized fromnitrobenzene. It is a light yellow col ored solid melting at about 330C.

Example 4 By the substitution of an equivalent gram molecular Weight ofN bromoacetyl-N-methyl-lamino 4 hydroxyanthraquinone forN-bromoacetyl-N-methyl-l-aminoanthraquinone in Ex- As indicatedhereinbefore the N-halogenoacetyl N alkyl 1 aminoanthraquinone compoundsemployed in the process of my invention, where corresponding, can beused interchangeably. ThusN-chloro-acetyl-N-methyl-l-aminoanth'raquinone or N-iodoacetyl N methyl1 aminoanthraquinone can be used in place of'N- bromoacetyl Nmethyl-l-aminoanthraquinone. TheN-halogenoacetyl-N-alkyl-l-amino-anthraquinone compounds as well as the1-nitro-3- alkylanthrapyridone compounds of 'my invention are lightyellow colored solids.

While the process of my invention has been described more particularlywith reference to the use of Cellosolve or fi-hydroxyethyl acetate asthe liquid diluent it is to be understood that other suitable diluents,such as those specifically indicated as being suitable, can be used.

Attempts to effect ring closure using N-propionyl N methyl 1aminoanthraquinone, N-CO(CH2)iCOOCzHs-N-methyl 1 aminoanthraquinone andN bromoacetyl-N-n-butyl 1 aminoanthraquinone were unsuccessful.Similarly attempts to effect ring closure withl-halogenoacetaminoanthraquinone compounds containing no alkyl group onthe amino nitrogen atom in the 1 position were unsuccessful. Thus1-chloro-acetaminoanthraquinone was recovered with unchanged meltingpoint (222 C.) after treatment in accordance with the process of myinvention.

The N -halogenoacetyl-N alkyl 1 aminoanthraquinone compounds can beprepared by reacting a l-alkylaminoanthraquinone with a compound such aschloroacetyl chloride, bromoacetyl bromide or iodoacetyl chloride inknown fashion. A number of these compounds such as N- bromoacetyl Nmethyl-l-aminoanthraquinone, N chloroacetyl Nmethyl-l-aminoanthraquinone, N -iodoacetyl-N-methy1 1 aminoanthraquinone and N-bromoacetyl-N-methyl-leamino- 4-bromoanthraquinone areknown compounds. The methods used for the preparation of these knowncompounds can be used in preparing other N halogeno acetyl-N-alkyl-1-aminoanthraquinone compounds. To illustrate, N-bromo-acebyl-N-ethyl-l-amino anthraquinone, N bromoacetylN-methyl-1-amino-4-hydroxyanthraquinone and Nbromoacetyl-N-methyl-l-amino-5- hydroxyanthraqulnone can be prepared byreacting bromoacetyl bromide with l-ethyl-aminoanthraquinon'e,l-methylamino 4 hydroxy anthraquinone and1-methylamino-5-hydroxyanthraquinone, respectively. Similarly, N-chlorb'aeetyl-N-methyl 1 amino 5-bromoanthraquinone and N iodoacetyl N methyl-IaminO-S- bromoanthraquione can be prepared by reacting 1 methylamino 5bromoanthraquinone with Example A.Preparation of N-chZo'roacetyZ-N-methyl-1 -amz'7'z0ltnthraquinone Example B.-Preparation ofN-bromoacetyZ-N- methyl-1 -amino- 4-bromoanthmquinone This compound wasprepared by refluxing for 20 minutes a mixture of 20 grams ofl-methylamino-4-bromoanthraquinone, 159 cc. of xylene, and 15 .cc. ofbromoacetyl bromide. The initial red color of the reaction mixturebecame yellow. The hot reaction mixture was filtered and N- bromoacetyl-N -methyl- 1 -amino-4-bromoanthraquinone crystallized from thefiltrate on cooling as a light yellow colored solid. It melted at 162 C.0

Analysis: Calculated. for ClvHmBrNOsz Br, 22.3. Found: Br, 22.2.

Example C.-Prepamtion of N-chloroacetyl-N- methyl-1-amino--bromoanthraquinone This compound was prepared by refluxing for20 minutes a mixture of 20 grams of l-methylamino-4-bromoanthraquinone,150 cc. of benzene, and 15 cc. of chloroacetyl chloride. The red colorof the reaction mixture became yellow. The hot reaction mixture wasfiltered and N- chloroacetyl-N-methyll-aminolbromoanthraquinonecrystallized from the filtrate on cooling. It was obtained uponrecrystallization from ethylene glycol monoethyl ether as a light yellowcolored solid melting at 233 C.

The 1-alky1aminoanthraquinone compounds are either known or can beprepared by introducing an alkylam'ino group into an alpha position ofthe anthraquinone nucleus by known methods. 1-amino-4hydroxyanthraquinone, l amino-5- hydroxyanthraquinone, 1 amino 4bromoanthraquinone, l amino 4 chloroanthraquinone and 1-amino-5chloroanthraquinone, for example, are known compounds and by introducingan alkyl group into the amino group of these compounds a wide variety ofl-alkylaminoanthraquinone compounds can be obtained.

As previously indicated the new 1-nitro-3-alkylanthrapyridone compoundsof my invention are useful as intermediates for the preparation ofanthrapyri-done dye compounds having known utility. The l-nitro groupreadily undergoes replacement, for example, by an alkylamino or anarylamino group. The following examples illustrate the replacementreaction.

Example D recover the l-p-toluidino 3 methylanthrapyri done formed inthe reaction. After recrystallization from a benzene-methanol mixturethe deep yellow reaction product melted at 239 C.

Analysis Calculated for C24H1sN2O22 C, 78.7; H, 4.9; N, 7.7. Found: C,78.5; H, 5.2; N, 8.1.

Errample E 23 grams of 1-nitro-3-methyl-ti-bromoanthra-v pyridone, 1gram of sodium acetate, a trace of copper acetate, and 30 cc. ofp-toluidine were heated together with stirring for 4 hours at 168- C.The 1,6-di-p-toluidin-o-3-methylanthrapyridone formed in the reactionwas recovered by filtration and recrystallized from hot benzene. Itmelts at 246 C.

Analysis: Calculated for C31I'I25N302I Found: N, 9.0.

It will be understood that the nitro group can be replaced by otherarylamine compounds such as aniline, o-toluidine, m-toluidine,o-chloroaniline, m-chloroaniline, p-chloroaniline, o-bromoaniline,m-bromoaniline, p-bromoaniline, 0-, mand p-anisidine, p-ethylaniline or1-arninoanthraquinone. Alkylamines such as methylamine, ethylamine,n-propylamine, n-butylamine and n-amylamine, for example, can also beused to replace the nitro group with an alkylamino group.

The l-nitro group of my compounds can also be reduced to form al-aminoanthrapyridone compound. Thus 1-nitro-3-methylanthrapyridone canbe reduced to 1-amin0-3-methylanthrapyridone which can be used as anintermediate for vat dyes. This latter compound can be treated withbenzoyl chloride to form 1-benzamido-3-methylanthrapyridone.

Upon sulphonation of the 1-arylaminoanthrapyridone andl-alkylaminoanthrapyridonecompounds by known methods, e. g. withsulphuric acid monohydrate or weak oleum sulphonate d dye compoundswhich are useful for the coloration of wool are obtained. Thenon-sulfonated compounds possess some utility for the coloration ofcellulose acetate when applied thereto in finely divided condition froman aqueous dispersion.

I claim:

1. A process for the manufacture of new anthrapyridone compounds whichcomprises reacting an anthraquinone compound having the general formula:

wherein R represents an alkyl group having one to two carbon atoms, Xand Y each represents a member selected from the group consisting of ahydrogen atom, a halogen atom and a hydroxy group and Z represents amember selected from the group consisting of a. bromine atom, a ch10-rine atom and an iodine atom with an alkali metal nitrite in thepresence of a liquid diluent which exerts a solvent action on theanthraquinone com ound and is inert with respect to the reaction mixtureand recovering the anthrapyridone compound formed.

2. A process for the manufacture of new anthrapyridone compounds whichcomprises react- 7 ing an anthraquinone compound having the generalformula:

wherein X and Y each represent a member selected from the groupconsisting of a hydrogen atom, a halogen atom and a hydroxy group and Zrepresents a member selected from the group consisting of a bromineatom, a chlorine atom and an iodine atom with an alkali metal nitrite inthe presence of a liquid diluent which exerts a solvent action on theanthraquinone compound and is inert with respect to the reaction mixtureand recovering the anthrap lidone compound formed.

3. A process for the manufacture of new anthrapyridone compounds whichcomprises reacting an anthraquinone compound having the general formula:

(II) N\ wherein X represents a member selected from the group consistingof a hydrogen atom, a halogen atom and a hydroxy group and Z representsa member selected from the group consisting of a bromine atom, achlorine atom and an iodine atom with an alkali metal nitrite in thepresence of a liquid diluent which exerts a solvent action on theanthraquinone compound and is inert with respect to the reaction mixtureand recovering the anthrapyridone compound formed.

4. A process for the manufacture of 1-nitro-3- methylanthrapyridonewhich comprises reacting an N-monohalogenoacetyl-N-methyl 1aminoanthraquinone, wherein halogeno represents a member selected fromthe group consisting of a bromine atom, a chlorine atom and an iodine 7atom, with an alkali metal nitrite in the presence of a liquid diluentwhich exerts a solvent action on the anthraquinone compound and is inertwith respect to the reaction mixture and recovering the1-nitro-3-methyl-anthrapyridone formed.

5. A process for the manufacture of 1-nitro3- methyl-anthrapyridonewhich comprises reacting N-bromoacetyl-N-methyl-l-aminoanthraquinonewith sodium nitrite in the presence of a. liquid diluent which exerts asolvent action on the N- bromoacetyl-N-methyl 1 aminoanthraquinone andis inert with respect to the reaction mixture and recovering the1-nitro-3-methyl anthrapyridone formed.

6. The anthrapyridone compounds having the general formula:

wherein R represents an alkyl group having one to two carbon atoms and Xand Y each represents a member selected from the group consisting of ahydrogen atom, a halogen atom and a hydroxy group.

7. The anthrapyridone compounds having the general formula:

II C OzN- CH3 i Y o X wherein X and Y each represents a member selectedfrom the group consisting of a hydrogen atom, a halogen atom and ahydroxy group.

8. The anthrapyridone compounds having the general formula:

